Cycloparaffin polymer coating compositions



otented July 3,,

, 2.379.606 CYCLOPARAFFIN POLYMER COATING COMPOSITIONS Robert C. Swain, Riverside. and Pier-repent Adams, Stamford, Conn., asslgnors to American Cyanamid Company, NEWYOlk, N.

ration of Maine 3., a corpo- No Drawing Application September 25, 1940, Serial No. 358,282

4 Claims. (o1. 260-42) This invention relates to coating compositions containing hydrocarbon polymers of the cyclotype and melamine-formaldehyde resins.

An object of this invention is to improve the physical and chemical properties of coating -compositions containing hydrocarbon polymers of the cycloparefin type, e. g., color stability,

' resistance tosolvents, etc.

Another object .of'this invention is to provide compositions containing hydrocarbon polymers of the cycloparafin' type and compatible proportions of compatible melamine-formaldehyde resins.

These and'other objects are attained by blending one part of hydrocarbon polymer of the cycloparafin type with about one part or more of e. melamine-formaldehyde resin which has I been elh'leted with a. butyl alcohol and wherein the molsl ratio of formaldehyde to melamine is at leest about 4:1.

I The following examples in which the proportions are: in parts by weight are given by way of fllustration and not in limitation. The $3 310". par-emu polymer used in the following examples is one obtained by hydrogenation of essentially. indene" polymers (or polymers of mixtures of indene and some coumerone) sold under the trade name of Nevillite #2, having a. melting point between about 145-155 C. and being prepared in accordance with the procedureset forthby Cnrmody et al. in "Industrial and Engineering Chemistry, vol. 32, pages 6844592, N. B." page 891.

Example 1 v Parts Melamine-formaldehyde resin A 50 Cycloperamn polymer ("Nevillite #2) 50 Example 2 r 9 Parts Melamine-formaldehyde resin "B 75 Cycloparafiin polymer (.Neviliite #2) A composition containing these. ingredients isprepared by admixing 150 parts of melamineformaldehyde resin. B solution resin) with 50 parts of Cycloparafiin polymer stock solution. Films of the composition are applied to metal objects and baked at a temperature of about 135 C. for about one-half hour. A clear, tough him is formed.-

.Emample 3 Parts Melamine-formeldehyde resin A Q0 Cycloparaflln polymer .(Nevillite #2) 10 A composition containing these ingredients is prepared by admixing 180 parts of melamine-- formaldehyde resin A solution (50% resin) with 20 parts of Cycloparafiln polymer stock solution. Films of the composition are. applied to metal objectsand baked at a. temperature of about 135 C. for about one-half hour. The product formed is a very hard, clear coating.

Example 4 Melamine-formaldehyde resin 0 Cycloparafiin polymer '(Nevillite #2f)- about 135 C. for about one-half hour. A waterwhite film having good chemical properties is formed.

' Example 5 I Parts Melamine-formaldehyde resin C Cyclopcrafinpolymer- (Nevillite #2) A composition containing these ingredients is prepared by admixing 180 parts ofmelamine- I formaldehyde resin C solution (50% resin) with 20 ports of Cycloparamn polymer stock solution. Films of the composition are app ied to metal objects and baked at a temperature of about C. for about one-helfhour. A hard, transparent 'fllm is produced. I

' Preparation of melamine-formqldehyde ,resin "4 Parts Melamine (1 mol) 126 Formelin (*i'mols) (37% formaldehyde in.

water) 324.4 n-Butano1 440 This mixture-isplaced in t reflux apparatus Formalin (6 mols) (37% formaldehyde in 1 able water trap through which the reflux condensate passes on its return to the reaction chamber and in which the essentially aqueous fraction of the condensate may be' separated from the essentially non-aqueous fraction and means is provided so that the former fraction may be drawn oil if desirable. The reaction mixture is refluxed at a temperature of about 91-93" C. at atmospheric pressure for 6-12 hours. The water is removed by azeotropic distillation from the reaction mixture during the reflux operation beginning preferably after about 2-5 hours have elapsed and the water so removed is separated from the reflux condensate in the water trap. During the distillation about 550 additlonal parts of butanol are added gradually. When the reflux condensate is substantially anhydrous the vapor temperature will be about 100-105 C. The pressure is lowered sufficiently toreduce the vapor temperature to about 85-90 C. andthe resin solution is concentrated to about 60-70% solids by vacuum distillation. The resulting resin solution may be diluted to about 50% solids with any desired solvent or diluent, e. g., xylene.

Preparation of melamine-formaldhyde resin "B" Parts Melamine (1 mol) 1 26. Formaline (5 mols) (37% formaldehyde in water) n-Butanol 440 This mixture is placed in a reflux apparatus which is provided with a condenser and a suitable water trap through which the reflux condensate passes on its return to the reaction chamber and in.

which the essentially aqueous fraction of the condensatemay be separated from the essentially non-aqueous fraction and means is provided so that the former fraction may be drawn of! if desirable. The reaction mixture is refluxed at a temperature of about 91-93 C. at atmospheric pressure for 6-12 hours. The water is removed by azeotropic distillation from the reaction mixture during the reflux operation beginning preferably after about 2-5 hours have elapsed and the water so removed is separated from the re-. flux condensate in the water trap. During the distillation about 550 additional parts of butanol are added gradually. When the reflux" condensate is substantially 'anhnldrous the vapor temperature willbe about 100-105 C. The pressure is lowered sufliciently to reduce the vapor temwhich is provided witha condenser and a suitsirable. The reaction mixture is refluxed at a temperature of about 91-93 C. at atmospheric pressure for 6-12 hours. The water is removed by azeotropic distillation from the reaction mixture during the reflux operation beginning prelerably after about'2-5 hours have, elapsed and the water so removed is separated from the reflux condensate in the water trap. During the distillation about 550 additional parts of .butanol are added gradually. when the reflux condensate is substantially anhydrous the vapor temperature will be about 100-105" C. The pressure is lowered suficiently to reduce the vapor temperature to about 85-90 C. and the resin solution is concentrated to about 60-70% solids by vacuum distillation. The resulting resin solution may be diluted to about 50% solids with any desired solvent or diluent, e. g., xylene.

. Cycloparaflin polymers suitable for use accord: ing to our invention may be prepared by hydrogenating indene polymers, indene-coumarone polymers, coumarone polymers,'etc. and they may also be produced by polymerizing various mixtures of unsaturated compounds of'the cyclohexane series and the cyclopentane series. Such unsaturated materials may contain not only monooleflnes, but diolefines and they may be polymerized by the use of suitable catalysts such as boron trifluoride, aluminum chloride, sulfuric acid; etc. Preferably products suitable for our invention are essentially hydrogenated indene polymers having a melting point between about 145 and about 160 C.- The preparation of products of this type is described by Carmody et a1. loc. 'sit., Patents Nos. 2,128,985, 2,128,984, 2,139,722 (See especially either simultaneously with dehydration or subse-' Generally the simultanequent to dehydration. ous condensation of melamine, formaldehyde and a suitable alcohol is used because of convenience.

The condensation may be carried out either with perature to about 85-90? C. and the resin solution isconcentrated to about -70% solids by vacuum distillation. The resulting resin solution may be diluted to about 50% solids with any do.-

sired solvent or diluent, e. g., xylene.

Preparation of melamine-formaldehyde rsin 0" Parts Melamine (1 mol) 126 water) n-Butanol m 440 or without an acid catalyst and in some instances basic catalysts may desirably be utilized.

The melamine-formaldehyde resins vary slightly according to minor variations of control during their production and in some instances small proportions of a suitable solvent material, e. 8., benzene, xylene, toluene, acetone, etc., may be added to the original solutions of hydrocarbon 1 polymers and melamine-formaldehyde resin in order to produce perfectly clear solutions if such solutions are not originally obtained.

While formaldehyde has been used in the previous examples, it will be obvious that other aldehydes such as the various polymers of formaldehyde, e. g., paraformaldehyde, or substances which yield formaldehyde may be used in place of part r all of the formaldehyde.

The elamine-formaldehyde resins may be alkyla with-n-butyl alcohol as in the above ex-.

ampls or they may be alkyla'ted with other butyl alcohols or mixtures of butyl alcohols. Melamine-formaldehyde resins which-are alkylated with alcohols other than the butyl alcohols may also be blended with hydrocarbon polymers of the cycloparaflin type in some instances. We

.have found that a melamine-formaldehyde resin having a ratio of formaldehyde to melamineof about 5:1 and alkylated with hexylalcohol is compatible with up to about 10% of the hydrosolids weight basis).

carbon polymers of the cycloparaflln type have been found to be compatible with'melamineformaldehyde resins wherein the molal ratio of formaldehyde to melamine is about :1 up to 6:1 irnot more than about 1 part of the hydrocarbon polymer is blended with 1 part or mel-- amine-formaldehyderesin. In some instances, other ratios oi formaldehyde to melamine may be employed. For example, a melamine-forms aldehyde resin which is butylated and wherein the molal ratio of formaldehyde to melamine is about 3:1 is compatible with the hydrocarbon polymer in proportions up to about 10% (total Relatively small proportions of melamine-formaldehyde resins wherein the molal ratio of formaldehyde to melamine is about 6:1 are compatible with the hydrocarbon- .polymers of the cycloparailln type as described and claimed in our copending application Serial No. 358,283 entitled Coating compositions containing cycloparaiiin type polymers. We have found that resins wherein the ratio of formaldehyde to melamine is 5:1 or less .are generally incompatible with hydrocarbon polymers of the cycloparaflln type in proportions less than about 50% (total solids weight basis). While ratios of formaldehyde to melamine higher than 6:1 may be used, it is generally undesirable inasmuch as formaldehyde is lost during the curing so that usually the product in its cured condition does not contain more than about 6 mole of formaldehyde to 1 mol of melamine.

As indicated above thehydrocarbon polymers of the cycloparailin type are blended with the melamine-'-formaldehyde resins in proportions ranging upwards from about 50% (total solids weight basis) 01' melamine resin.

Our-compositions may be used in admixture with other resinous compositions, e. -g., ureaiormaldehyde resins, phenol-formaldehyde res ins, nitrocellulose, ester gum, etc. They may also be used in drying oil and the like. I

A wide variety of plasticizers may be incorpovehiclessuch as linseed oil rated into our products such as the alkyl phthaiates, tricresyi phosphate, some modified alkyds,

etc.

Various fillerapigments, dyes and lakes may be added to our compositions, e. g., lithopone, zinc the melamine-formaldehyde resins or to enable the resin to be cured at lower temperatures than indicated in the above examples. Such substances are, for instance, phosphoric acid, ammonium salts or phosphoric acid, etc.

Films of our mixed hydrocarbon polymers and alkylated melamlne tormaldehyde resins are useml in varnishes, lacquers and other coating compositions. Such compositions are very resistant to corrosive and weathering conditions, as well as I being resistant to acid and alkali, thereby rendering them especially suitable for use in coatirm compositions, particularlyconcrete enamels and various interior finishes. Our compositions are substantially odorless and tasteless and therefore are of use as protective coatings for food and beverage containers.

One advantage of our melamine-formaldehyde resin-hydrocarbon. polymer mixtures of especial importance is in the reduced solubility and thermoplastieity' as compared to compositions containing only cycloparaflln type polymers.

Obviously many modifications and variations in the processes and compositions described above may be made without departing from the spirit and scope or the invention as defined by-the appended claims. I

We claim:

1. A coating composition containing a solid hydrocarbon polymer of the cycloparaflln type, ob-

, tainedby hydrogenating a substance" selected from the group consisting of coumarone polymers, indene polymers and mixed coumarone-indene polymers, and a melamine-formaldehyde resin which has been-reacted with a'butyl alcohol,

- wherein the molal ratio of formaldehyde to melfrom the group consisting of coumarone poly-' mers, indene polymers and mixed coumaroneindene polymers, and melamine-formaldehyde resin which has been reacted with n-butyi alcohol, wherein the molal ration of formaldehyde to melamine is at least about 4:1 and wherein the ratio of melamine resin to hydrocarbon polymer is at least about 1:1.

, 3. A coating composition containing a solid hydrocarbon polymer of the cycloparaflin typ obnil tained by hydrogenating materials which are essentially polymerized indene. and melamineformaldehyde resin which has been reacted with n-butyl alcohol, wherein the molal ratio of formaldehyde to melamine is'at least about 4:1 and v wherein the ratio of melamine resin to hydrocarbon polymer is at least about 1 1.

4. A coating composition containing a hydrocarbonpolymer of the cycloparaflln type, ob-

tained by hydrogenating a substance selected from the group consisting of coumarone poly-.

mers, indene polymers and mixed coumaroneindene polymers, and having a melting point hetween about and C. and melamine-formwherein the .ratio of melamine resin to hydro-' carbon polymer is at least about 1: 1.

ROBERT c. swam. PN'I' spams, 

